DE2802984A1 - VULCANIZABLE RUBBER MIXTURES AND METHOD FOR BONDING RUBBER TO REINFORCEMENT MATERIALS - Google Patents

Description

uZ: M 543
Case: 55 971

SUMITOMO CHEMICAL COMPANY, LIMITED
Osaka, Japan
10

"Vulcanizable rubber compounds and methods of bonding of rubber with reinforcing materials "

For the production of items made of rubber, such as vehicle tires, Belts and hoses, rubber must be reinforced with reinforcing materials, with the adhesion between the rubber and the reinforcement material is often unsatisfactory.

The bonding of rubber or rubber with such reinforcing materials was previously usually done by pretreating the reinforcement materials with certain adhesives. With increasing demand for high quality, i.e. very well bonded objects, in recent years the interest of the relevant industry was drawn more and more to so-called "compounding adhesion". With this procedure certain chemical substances are incorporated into the rubber together with other components, whereby a good bond between the reinforcement material and the rubber is achieved during vulcanization, regardless whether or not the reinforcement material has been pretreated with an adhesive.

The above procedure includes the following two

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the process variants. According to one variant v / earth in the rubber

(a) a formaldehyde acceptor, such as an m-disubstituted one Benzene, for example resorcinol, m-aminophenol or a

.5 reaction product of resorcinol and formaldehyde, such as a resorcinol resin, and

(b) a formaldehyde donor, which by heating in the rubber Forms formaldehyde,

incorporated. According to the other variant, rubber is vulcanized onto a steel cord, with a halogen acceptor, such as an m-disubstituted benzene, for example resorcinol, m-aninophenol or a resorcinol resin, as well as a halogen donor ^ such as tetrachloro-p-benzoquinone, an N, N-dihalogenated aromatic Sulfonamide or a cyclic N-halogenated amide, be used as components of the rubber mixture.

However, the aforementioned procedures are unsatisfactory and need to be improved. For example, the use of m-disubstituted benzenes, such as resorcinol or m-aminophenol, leads to the formation of unpleasant haze during the incorporation of these compounds into the rubber at a high temperature, usually at a temperature of over 110 ^° C., in order to ensure a uniform distribution of the To achieve connection in rubber. This method thus leads to environmental pollution. In addition, when the rubber treated in this way is left to stand, the previously incorporated compounds, for example resorcinol or m-aminophenol, bloom. This blooming leads to non-uniform adhesion between the rubber and the reinforcing material, with the consequence of a rather poor quality of the rubber articles produced.

To solve these problems, instead of / resorcinol and m-

Aminophenol as acceptors so-called resorcinol resins are proposed, which are produced by condensing resorcinol with formaldehyde can be obtained. Such a resorcinol resin is essentially

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dimer, trimer or tetramer and is so different from resorcinol or m-aminophenol. The disadvantages of these monomeric compounds such as the formation of haze during the incorporation into rubber or the blooming, are caused by the use of the Resorcinol resin significantly reduced. However, other new disadvantages are associated with gum formation. For example, is a Resorcinol resin of this type is highly hygroscopic and easily solidifies, making storage, weighing and incorporation clear be made more difficult. The resulting moisture content in the rubber is also often undesirable. Therefore exists The manufacturers, suppliers and users of resorcinol resins are very interested in the aforementioned disadvantages to eliminate.

It has been found that these disadvantages are eliminated by using a Polycondensate composed of an alkylphenol, formaldehyde and resorcinol can be largely avoided (cf. US Pat. No. 3,963,652). It was also found that the adhesion between rubber or rubber and a reinforcing material through use a copolycondensate which is very different from the aforementioned copolycondensate can be improved.

The copolycondensate according to US Pat. No. 3,963,652 is made by reacting of resorcinol with a prepolycondensate of an alkylphenol and formaldehyde and distilling off the water present in the reaction system after completion of the reaction manufactured.

Surprisingly, it has now been found that a copolycondensate with even better properties can be obtained if the water present in the reaction system is used during the reaction is distilled off between the prepolycondensate and the resorcinol and then the reaction product is solidified. It is also shown that this improved copolycondensate not only using that in the aforementioned patent called prepolycondensates from an alkylphenol and

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Γ "_ t% η η * ι η ό t '

Formaldehyde can be produced. Rather, any prepolycondensate produced from other than those described there Alkylphenols and acetaldehyde can be used instead of formaldehyde. It was also found that when reducing de3 ratio of resorcinol to alkylphenol in the copolycondensate with regard to its deliquescence

and improved in terms of blocking

becomes, but at the same time a deterioration of the adhesion occurs, as stated in the aforementioned patent.

On the other hand, according to the present invention, there is a copolycondensate with excellent adhesion without the undesirable Disadvantages of the deliquescence. And with regard to the

Blocking obtained, although the ratio of resorcinol is low is. Even if this ratio is large, copolycondensates are obtained according to the present invention, the opposite the copolycondensates known from the aforementioned patent not only have a significantly better adhesion / but are also significantly improved in terms of deliquescence and blocking.

It is not sufficiently clear why the differences in the processes according to the aforesaid patent and the present one Invention cause such different properties of the copolycondensates produced. It is believed, that according to the present invention in reacting the resol type prepolycondensate with resorcinol or m-aminophenol and at the same time distilling off the water present in the reaction system, the copolycondensate obtained is a Has structure in which resorcinol or m-aminophenol is selectively bonded to both ends of the prepolycondensate. Will on the other hand, the resol type prepolycondensate reacted with resorcinol in the presence of water, as in the aforementioned Patent specification takes place, the copolycondensate obtained has a structure in which the resorcinol or the m-

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Aminophenol only at one end of the prepolycondensate or at it middle part is tied. Such structural differences also have different properties of the products

Episode.
5

The invention is based on the object of using the adhesion between rubber or rubber and reinforcing materials to improve a corresponding copolycondensate, the copolycondensate from a. Phenol derivative and formaldehyde or acetaldehyde is produced.

This object is achieved by the invention.

The invention thus relates to that characterized in the claims Object.

The method characterized in claim 6 is a preferred embodiment for the production of copolyconsensates.

An essential feature of the process according to the invention for the preparation of copolycondensates is that the copolycondensation reaction of the resol type prepolycondensate derived from a monovalent phsnol derivative and resorcinol is carried out with simultaneous distilling off of water from the Heaktionss.system, this water before the beginning this implementation is present and is formed during this implementation.

Since the copolycondensation reaction of the prepolycondensate with resorcinol releases water, it is removed by distilling off Pumped water out of your reaction system. Accordingly is in the absence of a solvent, the reaction to form the desired resin is complete when none Water passes over. On the other hand, if a solvent is used, after the water has been distilled off also distilled off the solvent to achieve the desired

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-ίο-

To obtain resin. According to the invention, when used a solvent of this after the completion of the copolycondensation reaction distilled off, the solvent can be easily separated off without at the same time the condensation reaction continues as it does occasionally in the known method according to the aforementioned patent bsobacntat will.

This means that according to the patent specification mentioned above .10 known processes the polycondensation reaction of the prepolycondensate with resorcinol is done in the presence of water and it can be difficult to complete the reaction. Accordingly, the reaction continues even while the solvent is being distilled off, resulting in a An increase in the molecular weight of the resin and a rapid increase in the viscosity of the mixture leads to it being difficult to obtain stir or gel into an insoluble resin.

In contrast, according to the invention, the water becomes during the reaction distilled off from the reaction mixture, xby a rapid Increase in viscosity or gelation during concentration of the reaction mixture is avoided.

Another feature of the present invention is that the i-length of resorcinol is 0.7 to 1.5 equivalents, preferably 0.3 to 1.3 equivalents per equivalent methylol group of the prepolycondensate. When resorcinol is used in such an amount, the copolycondensate obtained has very good properties and is particularly suitable for 3. As an adhesive for incorporating into rubber, as an adhesive for Bonding of wood or metals and as a binding agent in the shell casting process.

If resorcinol is used in larger quantities than indicated above, the content of unreacted monomers in the resin produced increases, which then has the same disadvantages as the

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Has customary resorcinol resins mentioned at the outset. Will on the other hand Resorcinol used in amounts smaller than the aforementioned, the adhesion of the resin obtained is relatively poor.

Another feature of the method of manufacture according to the invention of copolycondensates is the use of resorcinol in an amount of 0.3 to 2.3 equivalents, "preferably 0.5 to 2 equivalents, per equivalent of the phenol derivative. 10

As stated in the aforementioned patent specification, in general insufficient adhesion of the resin is to be expected. if the resorcinol is used in a smaller amount than the phenol derivative, it has surprisingly been found, however, that according to the invention reliably a desired copolycondensate can be produced having sufficient adhesion though the resorcinol in a smaller amount is used as the phenol derivative.

If the resorcinol is used in a larger amount than indicated above, the resin obtained still has a certain adhesion, but shows other disadvantages with regard to disintegration and blocking.
Such resins are undesirable because of their poor shelf life and difficult handling.

The prepolycondensate of the phenol derivative of the general formula I can be prepared in the usual way. For example, it can be made by reacting one equivalent of the phenol derivative with 0.5 to 2.5 equivalents of formaldehyde or acetaldehyde at a temperature of 40 to 150 C in the presence an alkaline catalyst. A hydroxide or carbonate, for example, is suitable as a catalyst an alkali metal or alkaline earth metal, such as sodium, potassium, lithium, magnesium and calcium hydroxide as well as sodium, Potassium, lithium, magnesium and calcium carbonate.

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The resol type prepolycondensate obtained is compounded with a compound of the general formula II, for example with resorcinol or m-aminophenol in the specified amount and at the same time Distilling off the water from the reaction system implemented · The reaction can take place in the absence or presence of a solvent be performed. The use of an organic solvent is preferred in order to make the reaction uniform to let go. The most suitable are organic solvents that form an azeotropic mixture with water, and their mixture with water can be easily separated into an aqueous and a non-aqueous layer by cooling. Specific examples of suitable organic solvents are Benzene, toluene, xylene, cumene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, sec-butylbenzene, tert-butylbenzene, cymene and mesitylene.

There can also be those which form azeotropic mixtures with barrels Solvents are used, the mixtures of which with water do not completely separate, but essentially separate into one Separate the water-containing layer and a further layer essentially containing the organic solvent. Specific Examples of such solvents are η-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, tert-pentyl, n-hexyl, n-octyl and benzyl alcohol, methyl ethyl ketone, methyl isopropyl ketone, Methyl isobutyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 3-hexanone, n-dipropyl ether and n-dibutyl ether.

It is also possible to use a solvent which is miscible with water and thus forms an azeotropic mixture, since the Polycondensation reaction can also be carried out when both the solvent and the water by azeotropic Distillation can be separated and at the same time the solvent is added to the reaction system. Specific examples such solvents are methanol, ethanol, n-propanol, isopropanol, acetone and tetrahydrofuran.

L J

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The condensation reaction of the resol type prepolycondensate with the compound of the general formula II can be carried out in the absence of a catalyst. However, acidic catalysts such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid and p-toluenesulfonic acid are usually used. The reaction temperature is preferably in the range from kO to 20O ⁰ C.

If the softening point of the resin obtained is too low, difficulties arise because of blocking during storage of the resin, while if the softening point is too high, the resin can only be melted with difficulty by heating. The copolycondensate obtained in the invention has a softening point of 70 to I ^{1 0} C IO. This temperature range meets the above requirements.

The phenol derivative of the general formula I used as starting material for the preparation of the copolycondensate is phenol or a phenol derivative with one or more substituents, which are identical or different and each has an alkyl radical with 1 to 12 carbon atoms, an aryl radical with 6 to 12 carbon atoms or an aralkyl radical Represent 7 to 12 carbon atoms. Specific examples of such phenol derivatives are o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, p-tert-butylphenol, ptert. -Octylphenol, pn-Nonylphenol, p-Pheny! Phenol, p-Benzylphenol, p-Isopropylohenol, 3- ^T 'iethyl-5-isopropylphenol, p- (0 (-Methylbenzzyi) -phenol, 3-Methyl-6-tert. -butylphenol and p-ß-phenylethy! phenol.

In addition to formaldehyde and acetaldehyde, paraformaldehyde can also be reacted with phenol or the phenol derivative.

Specific examples of compounds of the general formula II are resorcinol, m-arenophenol, resorcinol monoacetate, resorcinol monopropionate, Resorcinol butyrate, Re sorcinmonome thy lether,

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ι Resorcinol monoethyl ether, resorcinol monopropyl ether and resorcinol monobutyl ether.

With regard to the pick-up ratio of the connections of the general -5 mean formula I and II in the aforementioned reaction, it should be noted that when using the compound of the general formula I in an amount of less than 25 üiolprozent the obtained Copolycondensate does have adequate adhesion, but at the same time has disadvantages such as haze formation from the monomers or blooming, which indicates the remaining unreacted compound of the general formula II in the copolycondensate is due. If the compound of the general formula I is used in an amount of more than 75 mol percent, Although the copolycondensate obtained does not show blocking caused by adsorption of moisture, it is the adhesion of the copolycondensate is lower. Therefore, the compounds of general formulas I and II are used in a molar ratio from 0.75: 0.25 to 0.25: 0.75 are used.

The copolycondensate according to the invention is incorporated into the rubber mixture usually in an amount of 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, per 100 parts by weight of rubber. The term "per 100 parts by weight of rubber" is hereinafter referred to as "PHR".

Compounds which form formaldehyde on heating (component II of the rubber mixtures according to the invention) are for example described in U3-PS 3 751 331. Specific examples are hexamethylenetetramine, di- or hexamethylolmelamines and their fully or partially etherified or esterified derivatives, oxazolidines, polyvalent methylolacetylene urea derivatives and N-methyl-1,3,5-dioxazine. These compounds are generally used in amounts from 0.3 to 10 PHR, preferably 0.5 to 5 PHR is used.

As component II of the rubber mixtures according to the invention

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also know, for example, p-benzoquinone derivatives, N, N-dihalogenates aromatic sulfonamides and cyclic N-halogenated amides are used, which in JP-OSes 34 679/74 and 99 579/74 are described. Specific examples of these compounds are tetrachloro-p-benzoquinone (hereinafter "Compound A"), NjNjN'jN'-tetrachloroxybis-coenzenesulfonamide) (hereinafter "Compound B"), naphthalene-1,5-di- (N, N-dichlorosulfonamide) (hereinafter "Compound C") and trichloroisocyanuric acid (hereinafter "Connection D").

As a rubber component in the rubber according to the invention Mixtures used rubber can be a natural or synthetic rubber, for example a styrene-butadiene copolymer, Polyisoprene, polybutadiene, acrylonitrile-butadiene copolymer or polychloroprene.

The reinforcing materials used according to the invention can organic reinforcement materials such as cotton, polyamide (nylon), polyester and rayon, or inorganic reinforcement materials, such as brass-plated steel wire, galvanized steel wire and glass threads.

Used as component II of the rubber mixtures according to the invention p-3enzochlnonderivate, Ν, Ν-dihalogenated aromatic sulfonamides or cyclic N-halogenated amides used, the rubber compounds prepared using these compounds are preferred for the compound of Rubber inserted with a steel wire. Other additives, such as carbon black, be incorporated. It can also use silica, silica anhydride and cobalt salts of organic acids can be used to improve the adhesion of the rubber compounds.

The copolycondensates of the invention, prepared by Condensation of a resol type prooly condensate (obtained from phenol or a phenol derivative and formaldehyde or acetone

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aldehyde) with a phenol derivative of the general formula II valuable intermediates for the production of the vulcanizable rubber compounds according to the invention.

The examples illustrate the invention, parts and percentages relate to weight, unless otherwise stated is.

example 1

A four-necked flask equipped with a reflux condenser and a thermometer is filled with 373 g of p-cresol, 373 g of toluene and 112 g of 88% paraforraaldehyde are charged. After heating to a temperature of 60 ° C, the mixture is at this 23.3 g of an aqueous 10N sodium hydroxide solution were added dropwise over the course of one hour. After completion After this addition the mixture is heated to reflux temperature and the reflux is maintained for 5 hours. 391 g of a solution of a prepolycondensate are obtained Resole type in toluene.

The resulting toluene solution contains 52% pesticides. The prepolycondensate of the resol type has 0.19 moles of kethylol groups per 100 parts.

The reflux condenser on the four-necked flask is replaced by a distillation condenser. The aforementioned reaction mixture is treated at a temperature of 6O ⁰ C and 192.5 g of resorcinol and 11.0 g of oxalic acid. After these compounds have completely dissolved, the temperature of the mixture is increased and the azeotropic mixture formed of water and toluene is distilled off. The separated toluene is returned to the flask, while the separated water is withdrawn from the reaction system, which ultimately leads to the complete separation of the water. After the water has been distilled off, the toluene is also distilled off. Finally, the reaction mixture is under reduced pressure (at most

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30 Torr) heated to a temperature of 150 ^{° C.} 630 g of resin A with a softening point of 104 ° C. are obtained.

Example 2 According to Example 1, using 324 g of p-cresol, 324 grams of toluene, 133 grams of SS percent paraformaldehyde, and 20.0 grams an aqueous 10N sodium hydroxide solution 301 g of a solution of a prepolycondensate of the resol type in toluene, wherein the reaction mixture is refluxed for 2 hours after the addition of the sodium hydroxide solution.

The toluene solution contains 54 % pesticides. The resol type prepolycondensate has 0.74 moles of i-ethylol groups per 100 parts by weight.
15th

The prepolycondensate is then reacted according to Example 1 using 330 g of resorcinol and 9.46 g of oxalic acid. 724 g of resin B with a softening point of 115 ^° C. are obtained.

Example 3 According to Example 1, using 216 g of p-cresol, 300 grams of toluene, 134 grams of SS percent paraformaldehyde, and 13.3 grams an aqueous 10N sodium hydroxide solution 633 g of a solution of a prepolycondensate of the resol type in toluene, the mixture being refluxed for one hour after the addition of the sodium hydroxide solution.

The toluene solution contains 51 % pesticides. The resol type prepolycondensate contains 1.12 moles of methylol groups per 100 parts by weight.

The prepolycondensate is reacted according to Example 1 with 447 g of resorcinol and 6.31 g of oxalic acid. 725 g of resin C are obtained

with a softening point of 117

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Example 4 According to Beisoiel 1, using 130 g of p-cresol, 243 g of p-tert-octylphenol, 377 g toluene, 107 g of paraformaldehyde and 38prozentigem l6,0 ζ 1ON aqueous sodium hydroxide solution 873 g of a solution of a resol type Preoolykondensats in toluene produced, wherein after the addition of the sodium hydroxide solution, the mixture is refluxed for 2 hours.

The toluene solution contains 52% solids. The resol type prepolycondensate contains 0.66 moles per 100 parts Methylolgruüpen, The prepolycondensate is according to Example 1 reacted with 264 g resorcinol and 7 * 57 g oxalic acid. You get 675 S of resin D with a softening point of 103 ° C.

Example 5

According to 3 example 1, using 351 g of p-tert-octylphenol, 351 3 toluene, 75 »4 g 33 percent paraformaldehyde and 11.3 S of an aqueous 10N sodium hydroxide solution 789 g prepared a solution of a prepolycondensate of the resol type in toluene, wherein after the addition of the sodium hydroxide solution the mixture is refluxed for 2 hours.

The toluene solution contains 52 % solids. The resol type prepolycondensate contains 0.40 moles of kethylol groups per 100 parts.

The prepolycondensate is made according to Example 1 with 187 g of resorcinol and 5.36 S oxalic acid reacted. 576 g of the resin are obtained Ξ with a softening point of 115 ° C.

Example 6

A four-necked flask according to Example 1 is charged with 329 g of phenol, 329 g of 3enzene and 134 g of 88% paraformaldehyde. After the dropwise addition of 20.3 g of an aqueous 5N sodium hydroxide solution over one hour at a temperature of 0O ⁰ C, the mixture is ^{heated to SO 0} C for 2 hours.

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heats. There are 813 g of a solution of a prepolycondensate obtained of the resol type in benzene.

The benzene solution contains 54 % solids. The resol type prepolycondensate contains 0.30 of methylol groups per 100 parts.

The prepolycondensate is reacted according to Example 1 with 190 g of resorcinol and 14.2 g of p-toluenesulfonic acid. 592 g of the resin P with a softening point of 98 ^° C. are obtained.

Example 7

A four-necked flask according to Example 1 is filled with 418 g of p-phenylphenol, Charged 418 grams of xylene and 92.5 grams of 88 percent paraformaldehyde. After the dropwise addition of 12.6 g of an aqueous 10η sodium hydroxide solution for one hour at a temperature of 60 C, the mixture is refluxed for 4 hours heated. 941 g of a solution of a prepolycondensate are obtained of the resol type in xylene.

The xylene solution contains 53 % solids. The resol type prepolycondensate contains 0.20 moles of methylol groups per 100 parts.

The prepolycondensate is reacted according to Example 1 with 102 g of resorcinol and 5.99 g of oxalic acid. 559 g of resin G are obtained with a softening point of 94 ° C.

Example 8

According to Example 1, using 337 g of p- ((X-methylbenzyl) phenol, 337 g of toluene, 81.2 g of 88% paraformaldehyde and 11.3 g of an aqueous 10N sodium hydroxide solution 767 g of a solution of a prepolycondensate of the resol type in Toluene produced, the mixture after the addition of the sodium hydroxide solution Is heated under reflux for 4 hours.

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The toluene solution contains 52 % solids. The resol type prepolycondensate contains a number of moles of 0.5 * 1 of methylol groups per 100 parts.

The prepolycondensate is reacted according to Example 1 with 137 g of resorcinol and 5-36 g of oxalic acid. Obtained 56I g of the resin H having a softening point of 103 ⁰ C.

Example 9

A four-necked flask according to Example 1 is charged with 366 g of 3,5-xylenol, 366 g of methyl isobutyl ketone and 102 g of SS percent paraformaldehyde. After the dropwise addition of 23.1 g of an aqueous 5N liatriumhydroxidlösung for one hour at a temperature of 50 C, the mixture is heated for 3 hours at 70 ⁰ C. 857 g of a solution of a prepolycondensate of the resol type in methyl isobutyl ketone are obtained.

The methyl isobutyl ketone solution contains 53% pesticides. The resol type prepolycondensate contains a mol of 0.4 * 1 of methylol groups per 100 parts.

The prepolycondensate is reacted according to Example 1 with 220 g resorcinol and 5> 7 g oxalic acid. 628 g of resin I are obtained

with a softening point of 112 ⁰ C.

Comparative example 1

891 g of a solution of a prepolycondensate of the resol type in toluene prepared according to Example 1 are added at a temperature of 6O ⁰ C with 115 g of resorcinol and 11.0 g of oxalic acid.

^3C) sets. After these compounds have completely dissolved, the mixture is refluxed for 6 hours. Then water and toluene are distilled off. The temperature of the mixture is then heated ^{to a temperature of 150 °} C. under reduced pressure (at most 30 torr). 56I g of resin J with a softening point of 137 ° C. are obtained.

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Comparative Example 2 As in Example 1, but shortening the time for the reaction between p-cresol and formaldehyde at the reflux temperature for one hour, 891 g of a solution of a Resole type prepolycondensate made in toluene.

The toluene solution contains 54 % pesticides. The Hesol type prepolycondensate contains 0.42 moles of methylol groups per 100 parts.
10

The prepolycondensate is reacted according to Example 1 with resorcinol. 553 g of resin K with a softening point of 1 JlI ⁰ C. are obtained.

Comparative Example 3 801 g of a solution of a prepolycondensate prepared according to Example 2 of the resol type in toluene are mixed with 330 g of resorcinol and 9.46 g of oxalic acid at a temperature of 60 ° C. After the compounds have completely dissolved, the mixture is refluxed for 6 hours. Afterward water and toluene according to Comparative Example 1 are distilled off. Kan receives 727 g of Resin L with a softener point of 145 ° C.

Comparative Example 4 A 1 liter four-necked flask is charged with 496 g of resorcinol and 243 g of water. After heating to a temperature of 70 ⁰ C, the mixture is added dropwise within one hour as with 203 g of an aqueous 37prozentigen Pormaldehydlösung added. After the addition is complete, the mixture is heated to 70 ° C. for 4 hours. After the reaction, the temperature of the reaction mixture is increased. As soon as the temperature reaches 100 ^° C., the distillation of water begins. Upon reaching a temperature of about 130 ⁰ G, the pressure in Koi-ben is gradually decreased. Finally, the temperature of the reaction mixture is reduced to at least 140 ° C

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Pressure (at most 30 torr) increased. Obtained 4l6 g of the resin M having a softening point of 10O ⁰ C.

Experiment 1 The adhesion of the examples 1 to 9 and the comparative examples 1 to 4 resins produced with regard to the adhesion of natural rubber to untreated polyamide threads (Nylon) or natural rubber on brass-plated steel wire determined in the following way:

A Banbury mixer is charged with 100 g of natural rubber, which is premixed for 1 minute. Then 45.0 g of carbon black (HAP black), 3.0 g of a plasticizer, 1.5 g of an antioxidant (ANTIGENS RD from Sumitomo Chemical Company, Ltd.) 2.0 g of stearic acid, 2.0 g of sulfur and 5.0 g of zinc oxide were added. The mixture is mixed for 2 minutes and then with 2.0 g of the resin to be tested, 0.7 g of a vulcanization accelerator (SOXINOL CZ from Sumitomo Chemical Company, Ltd.) and 2.4 s pentamethylol melamine trimethyl ether as a formaldehyde donor offset. The mixture is mixed for a further 1 1/2 minutes and then discharged.

The rubber mixtures obtained in each case are between 25.4 cm rollers transferred into plates of the required thickness and on the adhesion between the corresponding rubber and an untreated nylon thread (1260 d / 2) according to the H test (described in Indian Rubber World, 3d. 114 (March 1946), p. 213 to 219). The adhesion of the rubber to a measured steel wire (17.78 × 10.16 × 0.0173 cm) is also measured determined by the ASTM D-2229 method. The results are summarized in Table I below.

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- 23 Table I.

■ resin liability Guinmi / brassCer
Steel wire, kg according to the invention:
A.
B.
C.
D.
E.
F.
G
H
I. Rubber / polyamide
ks; / 9 mm 90 _; 5 *
92.4 *
94 _; 1*
95.3 *
90.7 *
92.1 *
92.2 *
90.1 *
93.6 * Comparison:
J
K
L.
M. 9.5
11.4
12.7
12.0
11.3
10.1
10.0
11.8
11.4 62.3
60.4
69.1
75.0 3, - ¹
6.1
8.4
10.8

+) Material breakage in the rubber

Attempt 2

The resins of Examples 1 to 9 and Comparative Examples 1 to ¹ J are prepared according to as tested for resistance to bleed and 31ocken follows:

The to be examined resin is up to a grain size of 0.074 mm pulverized, and in an amount of about 0.3 g of substantially uniformly spread in a tray in a constant atmosphere having a relative humidity of 65% at a temperature of ¹ IO ⁰ C. is left standing. Et?; A during a month, the amount of absorbed moisture and the blocking behavior of the resin is determined.

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The amount of absorbed moisture is determined according to the Karl Fischer method and given in " % moisture". The results are summarized in Table II. It can be seen from this table that the resins according to the invention, compared to resorcinol resins, absorb less moisture and have a better storage stability.

Table II

10

20 25 30 35

resin Amount of moisture absorbed, % 1 7th number of
14th Days
21 28 A. 0.4 0.6 0.8 1.0 1.1 B. 0.5 0.3 1.0 1.1 1.3 C. 0.7 1.0 1.4 1.7 ⁺⁾ 2.4 ⁺⁾ D. 0.5 0.7 0.9 1.2 E. 0.5 0.7 . 0.3 0.8 1.0 F. 0.6 o, a ⁿ , 9 1.1 1.1 G 0.4 0.5 0.8 0.8 0.9 H 0.4 0.6 0.9 1.0 1.0 I. 0.6 0.8 1.0 1.2 1.2 M. 3.1 7.4 10.4 11.5 11.8

With regard to blocking, resins A to E remain unchanged in all measurements, with the exception of resin C after 21 and 28 days this resin is a little sticky.

The resins F to I also remain unchanged with regard to blocking, while the resin M always blocks and is sticky.

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ExampleO

One equipped with a reflux condenser and thermometer Four-necked flask is filled with 324 g (3.19 mol) of p-cresol, 324 g of toluene, 133 g (3.9 mol) of 88 percent paraformaldehyde and charged 15 ml of aqueous 10N sodium hydroxide solution. The mixture is refluxed for 2 hours, yielding 801 g a solution of a prepolycondensate of p-cresol in toluene can be obtained.

After the reflux condenser on the four-necked flask has been replaced by a separator, the temperature of the mixture is adjusted to 00 ° C., and 220 g (2.0 mol) of resorcinol and 11 g of oxalic acid are added to the mixture. After these compounds have completely dissolved, the temperature of the mixture is increased. The prepolycondensate of p-cresol is reacted with resorcinol for 4 hours, with the azeotropic mixture of water and toluene that is formed being fed into the separator at the same time. The toluene is returned to the flask, while the water is discharged from the reaction system. After the reaction has ended, the toluene is distilled off. Finally, the mixture is ^{concentrated at a temperature of 150 °} C. under reduced pressure (at most 30 torr). It is a resorcinol / p-cresol / copolycondensate (resin 0) with a

Softening point of 104 ° C obtained. 25th

Examples 11 to 1 6

According to Example 10, but using that in the following Components listed in Table III, various copolycondensates (resins P to U) are produced. 30th

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- 26 Table III

5 ι
resin Connection of the general
mean formula I, κ aldehyde, g
(Mole) ~: (mole) Paraformaldehya
22.2 (0.65) l
Connection of all
common formula II,
g (mole) Resorcinol mono-
ethyl ether
77.4 (0.6) 10 ρ p-tert-octylphenol
20.6 (0.1)
p-cresol
43.2 (0.4) ■ Paraformaldehyde
22.2 (0.65) Resorcinol ·.
55 (0.5) Resorcinol
27.5 (0 ^. 25) 15th Q 3-methyl-5-iso-
propyiohenol
30 (0.2)
3,5-xylenol
61 (0.5) Acetylresorcinol.
45.6 (0.3) R. ρ- (a-methylbenzyl) -
phenol
119.4 (0.6) Acetaldehyde m-aminopnenol
39.1 (0.3): 43 _; 6 (0.4) 20th S. p-phenylphenol
42.5 (0.25) Paraformaldehyde resorcinol
23.6 (0.7) 32.5 (0.75) T phenol
13.8 (0.2)
m-isopropylphenol
27.2 (0 ^ 2) Paraformaldehyde
20.5 (0.6) U p-sec-9utvlohenol
37.5 (0 * 25)
p-cresol
54 (0.5) * 2
acetaldehyde
39.1 CO, 8)
:

⁺¹⁾ purity 33 %
⁺²⁾ purity 90 %

Comparative Example 5 Production of a copolycondensate from xylenol, p-tert-octylphenol and formaldehyde

One equipped with a reflux condenser and thermometer Four-necked flask is filled with 133.9 g (0.65 KoI) p-tert.-octylphenol, 206 g toluene, 23.6 g (0.7 KoI) 33 percent para

8Q9830 / 097S

Γ Π

formaldehyde and 8 ml of an aqueous 10η sodium hydroxide solution offset. The mixture is heated to a temperature of 70 ° C. for 3 hours and then 42.7 S (0.35 mol) of 3,5-xylenol are added. The mixture is allowed to react for a further 3 hours. Then water and toluene are used at the same time Temperature of 150 C under reduced pressure (max Torr) distilled off. The resin mentioned in the title (resin V) is obtained.

Comparative Example 6 Production of a copolycondensate according to Example 1 of FIG U.S. Patent 3,9o3,652

m-Cresol A 300 ml flask is charged with 32.4 g (0.3 mol) / J 48.6 g (0.6 mole) 37 percent formaldehyde and 3 ml (0.03 mole) one Filled aqueous IQn sodium hydroxide solution. The mixture

is heated to a Tenroeratur of 70 C for 3 hours and then 77 g (0.7 mol) of resorcinol were added. The mixture is allowed to react for a further 3 hours at a temperature of 50.degree.

After the completion of the reaction, the formed water becomes distilled off at a temperature of 120 C at a reduced pressure of 15 torr. A copolycondensate is obtained from Cresol, resorcinol and formaldehyde with a softening point of 92 ° C (resin W).

Comparative Example 7 Production of a resin from resorcinol and formaldehyde

A mixture of 110 g (1.0 mol) of resorcinol and 44.5 g of 37 percent formaldehyde is heated to a temperature of 70 ° C. for 5 hours in a 500 ml flask. After the reaction, the water formed is ^{distilled off at a temperature of 150 °} C. and a pressure of 25 torr. A resin composed of resorcinol and formaldehyde with a softening point of 9-3 ° C. (resin X) is obtained.

L -I

809830 / D97S

Γ Π

Example 7

In a 3anbury - "- 1 mixer (case temperature 120 to 130 C) different rubber compounds are produced in the following way:

100 parts of natural rubber four den premixed in the mixer for 1 minute and then with 45 parts of carbon black (HAF black), 3 parts a plasticizer, 1.5 parts of an antioxidant (ANTIGENE RD from Sumitomo Chemical Company, Ltd.), 2 parts Sulfur, 2 parts of stearic acid and 5 parts of zinc oxide were added. Mixing continues for 2 minutes. The mixture obtained Fird separately with 2 parts each of the resins prepared according to Examples 10 to Ib and Versrleichsbeispiele 5 to 7 (Resins 0 to X), 0.7 part of a vulcanization accelerator (SOXINOL CZ from Sumitomo Chemical Company, Ltd.) and 2.4 parts of pentamethylolmelamine trimethyl ether as a formaldehyde donor offset. The resulting mixtures are mixed for 1 1/2 minutes and then discharged.

The rubber compounds obtained are used converted into plates of the required thickness by 25.4 cn rollers. Then, according to experiment 1, the adhesion between rubber and an untreated nylon thread or a brass

ten steel wire determined. The vulcanization takes 20 minutes at a temperature of 150 ° C
are summarized in Table IV.

carried out at a temperature of 150 ° C. The results

809830/0979

- 29 Table IV

resin
ι I. Rubber / polyamide,
kg / 9 mm iaftung according to the invention: Rubber / brass-plated steel
wire, kg O 11.2 P " 12.5 85.5 * Q . 10.9 92.3 * R. 11.5 80.4 S. 13.8 T 13.0 92.1 * U 10.9 91.8 * Comparison: 90.0 * V 3.1 83.8 j W. 10.8 ■ v 10.6 61.2 74.3 69.8

+)

Material breakage in the rubber.

example 1

25 According to Example 17, but using the following components, v; earth various rubber compounds are produced.

Composition of the rubber compounds

SBR 1500 stearic acid silicon dioxide carbon black (HAF black) Vieichmaeher (aromatic) Zinc Oxide Antioxidant (ANTIGENS RD) Sulfur

100.0 Parts 2.0 Il 10.0 Il 50.0 ti 6.0 Il 5.0 It 1.5 Il 3.0 Il

809830/0979

Vulcanization accelerator (SOXINOL NS) Formaldehyde donor (hexamethylenetetramine) resin

1.2 parts 1.0 "2.0"

The mixtures obtained are described in Example 17 for their Checked adhesion properties. The results are in the table V summarized.

Table V

resin liability Rubber / brass-plated steel
wire, kg according to the invention: Rubber / polyamide,
kg / 9 mm O 86 _; 4 * ■ P. 11.5 89.3 * Q 13 _; 0 85.3 * R. 11 _; 5 88.8 * S. 12.0 SOjO * T 14 _; 0 85.6 * U 13.5 87.4 * Comparison: 11.5 V 72.4 W. 3.2 78 _; 5 X 11.8 54.3 11.5

Material break in rubber.

example

A mixture of 45 g (0.3 mol) of p-tert-3utylphenol, 43.6 g (0.6 mol) of 37 percent formaldehyde, 100 ζ toluene and 3 ml (0.03 mol heated for 3 hours on a Temoeratur of 70 ⁰ C) of an aqueous 1ON Natriunhydroxldlösung. The reaction mixture is then with 77 g

809830/0979

1 (0.7 mol) resorcinol are added and the mixture is heated to a temperature of 50 ° C. for a further 3 hours. After completion of the reaction v / ater and toluene are distilled off at a temperature of 120 ⁰ C and a pressure of 15 Torr. 132 g are obtained

5 of a copolycondensate of p-tert, butylphenol, resorcinol, and formaldehyde with a softening point of 92 ⁰ C (resin Y).

example

According to example 19, but using the in the following-10 the starting materials given in Table VI, various resins (resins Z-I to Z-5) are produced.

Table VI

resin Z-I Connection of all
common formula I,
g (mole) Aldehyde,
g (mole) Connection of all
common formula II,
g (mole) Z-2 p-phenylphenol
68 (0.4) formaldehyde
64.9 (0.8) Resorcinol mono-
acetate
91.3 (0.6) Z-3 p-crosol
21.6 (0.2)
3, '5-xylenol
24.4 (0.2) * 2
Acetaldehvd
34 _; 2 (0.7) Resorcinol
66 (0.6) Z-4 p- (a-methylbenzyl) -
phenol
59 _; 7 (0.3) *1
formaldehyde
73 ^ 0 (0.9) m-aminophenol
76.3 (0.7) Z-5 o-cresol
21.6 (0.2)
phenol
9.4 (0.1) Formaldehyde
56.8 (0.7) Resorcinol mono-
ethyl ether
96.5 (0.7) p-benzylnhenol
25 _; 3 (0.3) * 2
acetaldehyde
34.2 (0.7) Resorcinol
77 (0.7)

+1)

+2)

Purity 37 %

Purity 90%

809830/0979

100.0 PHR 2.0 Il 5.0 ■ I 45.0 ti 3.0 Il 3.5 Il 0.7 Il

1 Example 21

Resin Y (Example 19) and Resin Z-2 (Example 20) as well as Resin V (Comparative Example 14), Resin X (Comparative Example 16) and resorcinol (2 PHR in each case) and, as the second component, compound A (3 PHR) using 25.4 cm vials (surface temperature 9T ° C) incorporated.

10 basic mix

Naturkaut s chuk

Stearic acid

zinc oxide

RuS (HAF black)
15 plasticizers

sulfur

N-tert-butylbenzothiazylsulfenamide (vulcanization accelerator, SOXINOL NS)

2,2,4-tri: ethyl-1,2-dihydroquinone poly-1,5 merisat (antioxidant, ANTIGENE RD)

The rubber mixtures are tested for their adhesion between rubber and a brass-plated steel wire (17.78 × 10.15 × 0.0173 cm) according to the ASTM D-2229 method. The adhesion is determined as “initial adhesion” 24 hours after gluing by vulcanization and as “aging adhesion” after vulcanization with subsequent aging in a Geer oven at a temperature of 100 ^° C. for 48 hours. The results are summarized in Table VII below. The test specimens are produced at a temperature of 150 ^° C. for one hour. The stated measured values are mean values of 9 test specimens in each case. Blooming on the unvulcanized rubber compounds is also

809830/0979

judged with the naked eye. These results are also in the Table VII summarized.

Table VII

resin Liability, kg Old age liability 1
the end inventive
according to:
Y
Z-2 Initial adhesion 75.6
77.2 bloom Comparison:
Resorcinol
V
X 84.5
86.3 60.1
50.3
67.5 no
no Blank sample 63.4
57.3
75.8 48.3 Yes
no
no 54.3 no

Example22

(Ieil3 2 PHR, depending on?) Are given below in the base compound VIII respectively in the table below indicated components incorporated using 25.4 cm rolls (surface temperature of 100 ⁰ C), 25

Basic mixture of natural rubber S3R 1500 stearic acid 30 'zinc oxide

Carbon black (HA? Black) plasticizer sulfur

Vulcanization accelerator (SOXINOL NS) Antioxidant (ANTIGENS RD)

50.0 PHR 50.0 It 1.5 It 5.0 It 50.0 It 5.0 It 3.5 Il 1.0 Il 1.5 Il

809830/0979

According to Example 21, the mixtures obtained are tested for their adhesion between rubber and a brass-plated steel wire checks. The results are summarized in Table VIII.

Table VIII

resin Connection B
Il
Il
Il
Connection D
Il
Il
Il Blank sample Liability, kg Aging liability F. inventive
gamää:
ZI
Z-3
Z-4
Z-5
ZI
Z-3
Z-4
Z-5 Connection B
Il
Connection D
It Initial adhesion 74.8
75.2
74.1
73.6
71.6
73.1
70.3
73.1 Comparison:
V
X
V
X 36.3
35.3
32.3
33.3
33.4
33.6
35.6
34.5 45.2
50.5
43.3
52.6 56.3
63.5
5.3.3
61.9 42.3 50.1

Example23

The components listed in Table IX below (in each case 2 PHR) incorporated. The mixtures obtained xverden according to Example 21 for their adhesion between rubber and a measured one Checked steel wire. The results are summarized in Table IX.

809830/0979

- 35 -

Basic mix Natural rubber stearic acid zinc oxide RuS (HAF black) plasticizer sulfur

Vulcanization accelerator (SOXINOL NS)

Antioxidants (ANTIGENE RD)

Table IX

100 , 0 PHR 3 , 0 Il 5 , 0 ti 45 , 0 Il 3 , 0 If 3 , 5 Il 0 , 7 Il Λ IT Il

resin Connection B Liability, kg inventive Il Initial adhesion Aging liability according to: Il A. Il P. Il 91.8 82.3 Q Connection D 93.4 80.1 3 Il 92.8 82.1 U It 91.5 81.8 A. dd 90.8 84.3 P. Il 90.2 80.0 Q 39.6 79.8 S. Connection 3 90.0 80.1 υ Connection D 91.2 89.5 Comparison: 89.5 80.0 X Λ 75.3 69.5 74.2 68.2

Beisniel24

35 In the C round mix specified below, the Components specified in Table X below (2 PHR each)

809830/0979

incorporated. The mixtures obtained are with regard to the adhesion between rubber and a brass-plated steel wire checked according to Example 21. The results are summarized in Table X.

TTiis ching

SBR 1500 Stearic acid soot (HAF s chvi ar ζ) Plasticizer (aromatic) Sulfur Zinc oxide Antioxidant (ANTIGENE RD)

Vulcanization accelerator (SOXINOL NS)

Table X

100, 0 PHR 2, 0 Il 50, 0 Il 9, 0 Il 3, 0 Il 5, 0 It 1. 2 Il 1, 5 It

resin Connection B Liability, kg Aging liability invent. ^ s-
according to: ti Initial adhesion P. Il 80.1 Q ti 93.4 82.1 3 Connection D 92.3 81.8 U Il 91.5 84.3 P. Il 90.8 79.8 Q ti 89.6 80.1 90.0 89.5 U Connection B 91.2 80.0 Comparison: Connection D 89.5 X 69.5 X 75.3 68.2 74.2

809830/0971

Claims (1)

VjQSSIUS · VOSSIUS · HILTu · TAUCHNER ■ HEUNEMANN -j SIEBERTSTRASSE 4 8OOO MUNICH 86. PHONE: (O89) 474O75 CABLE: BENZOLPATENT MÜNCHEN -TELEX 5-29 4-5 3 VOPAT D January 24, 1978 5 oc; M 5 ^ 3 (Hi / ko)
Gases: 55 971 SUMITOMO CHEMICAL COMPANY, LIMITED
Osaka, Japan
10 "Vulcanisable rubber compounds and methods for gluing of rubber with reinforcing materials " ¹⁵ priorities: January 24, 1977, Japan, No. 6 978/77 January 26, 1977, Japan, No. 8 024/77 January 31, 1977, Japan, No. 10 107/77 Claims 1. Vulcanizable rubber compounds containing (I) a natural or synthetic rubber component, (ii) a compound which forms formaldehyde on heating or at least one a) p-benzoquinone derivative, b) N, N-dihalogenated aromatic sulfonamide in which the nitrogen atom of the sulfonamide group on two atoms 30 of the halogens chlorine, bromine and iodine and the sulfur atom of the sulfonamide group directly on the aromatic ring are bound, and / or c) cyclic N-halogenated amide in which the carbon atom the carbonyl group in the ring on two ³⁵ atoms are bonded and these nitrogen atoms to form a radical of the general formula -N-C-N- t Il 1 _L ZOZ 809830/0979 2802384 Jewells are bonded to a halogen atom, where Z represents a chlorine, bromine or iodine atom, and (III) a copolycondensate produced by condensation A) Resole type prepolycondensate obtained by Reacting at least one phenol derivative of the general formula I. OH Iu, '- ■ 3 ^ ₂ in which R ^, R ₃ and R, are identical or different and each represent a hydrogen atom, an alkyl radical having 1 to 12 carbon atoms, an aryl radical having 6 to carbon atoms or an aralkyl radical having 7 to carbon atoms, with formaldehyde or acetaldehyde in the presence of an alkaline Catalyst, with B) at least one phenol derivative of the general formula II ^0H in which X is a hydroxyl or amino group or a radical of the general formulas -0-CO-R ₁ J or -0-R ₅ , where R ₁ . and Rj- each represent an alkyl radical having 1 to 4 carbon atoms, the compounds of the general formulas I and II being used in a molar ratio of 0.75: 0.25 to 0.25: 0.75, distilling off the water present in the reaction system and then solidifying the reaction mixture. 2. Mixture according to claim 1, characterized in that the copolycondensate III is a solid copolycondensate, produced by reacting at least one Tnenol derivative of the general formula I with 0.5 to 2.5 equivalents of form 809830/0973 aldehyde per equivalent of the phenol derivative in the presence of one alkaline catalyst to a prepolycondensate of the resol type, which contains essentially no unreacted formaldehyde, and subsequent condensation of the obtained pre- -5 polycondensate with 0.43 to 2.3 equivalents of resorcinol or or m-aminophenol per equivalent of the phenol derivative of the general Formula I, wherein the resorcinol or m-aminophenol in an amount of 0.7 to 1.5 equivalents per equivalent of methylol groups of the prepolycondensate is present, and distilling off the water present in the reaction system. 3. Process for bonding rubber to reinforcing materials by applying a vulcanizable rubber mixture to an untreated or pretreated reinforcement material and vulcanizing the rubber mixture, characterized in that that a rubber mixture according to claim 1 begins. 4. The method according to claim 3, characterized in that a rubber mixture according to claim 2 is used. t process for the production of a solid copolycondensate, characterized by that one (A) Resole type prepolycondensate prepared by reacting at least one phenol derivative of the general type Formula I with formaldehyde or acetaldehyde in presence an alkaline catalyst, with (B) at least one phenol derivative of the general formula II condensed, using the compounds of the general formulas I and II in a molar ratio of 0.75: 0.25 to 0.25: 0.75, the water present in the reaction system is distilled off and then the reaction mixture is solidified. 6. The method according to claim 5, characterized in that a phenol derivative of the general formula I with 0.5 to 2.5 809830 / Ü979 Equivalents of formaldehyde per equivalent of phenol derivative in the presence of an alkaline catalyst to form a prepolycondene sat of the resol type, which contains essentially no unreacted formaldehyde, the prepolycondensate obtained with 0.43 to 2.3 equivalents of resorcinol or m-aminophenol per Equivalent of the phenol derivative of the general formula I, where 0.7 to 1.5 equivalents of resorcinol or m-aminophenol present per equivalent of methylol groups of the prepolycondensate, and the water present in the reaction system is distilled off. 7. The method according to claim 5, characterized in that the condensation of the prepolycondensate with the Phenolderi vat of the general formula II is carried out in an organic solvent which forms an azeotropic mixture with water. 8. Copolycondensates produced according to the process of claim 5. 9 · Copolycondensates, produced according to the method according to Ansoruch 6. 8Q9830 / 0978